CN115501731A - For removing H from sulfur-containing gases 2 S absorption liquid, preparation method and application - Google Patents

For removing H from sulfur-containing gases 2 S absorption liquid, preparation method and application Download PDF

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Publication number
CN115501731A
CN115501731A CN202110631321.1A CN202110631321A CN115501731A CN 115501731 A CN115501731 A CN 115501731A CN 202110631321 A CN202110631321 A CN 202110631321A CN 115501731 A CN115501731 A CN 115501731A
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China
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absorption liquid
triazine
present
sulfur
morpholine
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Inventor
余勇
陈小花
陈园园
宋丽
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1468—Removing hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/2041—Diamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20452—Cyclic amines containing a morpholine-ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2053—Other nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/504—Mixtures of two or more absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives

Abstract

The invention relates to a method for removing H from sulfur-containing gas 2 S absorption liquid and a preparation method and application thereof. The absorption liquid comprises the following components in percentage by weight: 10 to 18 wt.%, preferably 13 to 15 wt.% of triazine; 1 to 5 wt.%, preferably 2.5 to 4 wt.% of a sterically hindered amine; 0.1 to 1wt%, preferably 0.6 to 0.8wt% of an additive; and the balance water. Compared with the traditional desulfurization absorption liquid, the invention removes H 2 The S absorption liquid has high sulfur removal efficiency, large sulfur capacity and small using amount, and simultaneously has the performance of scale inhibition and corrosion inhibition, thereby achieving the purpose of improving economic benefit.

Description

For removing H from sulfur-containing gases 2 S absorption liquid, preparation method and application
Technical Field
The invention belongs to the field of gas purification, and particularly relates to a method for removing H from sulfur-containing gas 2 S absorption liquid, a preparation method and application.
Background
The sulfur-containing natural gas must be mixed with H 2 S and other sulfides can not enter a pipeline to be conveyed and used by downstream users after being removed to the corresponding technical standard (such as GB 17820-2018). For H in natural gas 2 The S removal has developed relatively complete process technology at home and abroad, and forms a process system mainly based on an alcohol amine absorption method and assisted by a wet oxidation method. These process technologies have better technical economy for the desulfurization and purification of natural gas with large sulfur potential, but for gas wells or stations with sulfur potential of less than 200kg/d, especially 50kg/d, especially in remote areas, offshore hydro-gas or space-limited low-H 2 In S gas wells and oilfield associated gas, the alcohol amine absorption method or the wet oxidation method has poor technical and economic feasibility, and even has insufficient space for building a device or cannot provide corresponding public engineering for the operation of the device. Thus, for low H 2 H removal of S natural gas or oil field associated gas 2 And under the S working condition, a desulfurizing agent and a related process which are different from the traditional absorption method need to be developed and used.
At present, triazine liquid removing agent is taken as the first technology for removing low-concentration hydrogen sulfide. 1,3,5-tri (2-hydroxyethyl) -hexahydro-s-triazine used for hydrogen sulfide removal has the characteristics of high absorption efficiency, small dosage, high speed, small pollution of absorbed products and the like, is widely used, but is easy to generate the problems of scaling and pipeline corrosion.
Disclosure of Invention
The invention aims at the defects of the prior art and provides a novel method for removing H from sulfur-containing gas (such as low-sulfur natural gas or low-sulfur oilfield associated gas) 2 And (3) an absorption liquid of S. The absorption liquid pair H 2 The S absorption effect is better than that of the traditional absorption liquid, the dosage is less, and simultaneously, the S absorption liquid has the performance of scale inhibition and corrosion inhibition.
To this end, the invention provides, in a first aspect, a process for removing H from a sulfur-containing gas 2 The absorption liquid of S comprises the following components in percentage by weight:
10-18 wt% of triazine;
1 to 5 wt.%, preferably 2.5 to 4 wt.% of a sterically hindered amine;
0.1 to 1wt%, preferably 0.6 to 0.8wt% of an additive; and
the balance of water.
In some embodiments of the present invention, the amount of triazine in the absorption liquid may be 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, or the like, in weight percent. In some preferred embodiments of the present invention, the triazine content in the absorption liquid is 13 to 15wt% in weight percentage.
In some embodiments of the invention, the triazine is 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
In other embodiments of the present invention, the hindered amine comprises at least one of a diazabicyclo ring and morpholine; preferably, diazabicyclo and morpholine are included.
The inventor of the present application found through research that the H pair of the absorption liquid can be increased by adding the sterically hindered amine to the absorption liquid 2 The amount of S absorbed and the rate of S absorption. Further, when the hindered amine includes both diazabicyclo and morpholine, the absorption performance of the absorption liquid can be optimized.
In some embodiments of the invention, the diazabicyclo ring is present in an amount of from 0.5 to 4.0wt%, based on the total weight of the absorption liquid. In some embodiments of the invention, the diazabicyclo ring may be present in an amount of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 3.0wt%, 4.0wt%, or the like, based on the total weight of the absorption liquid. In some preferred embodiments of the present invention, the diazabicyclic acid is present in an amount of 1.0 to 2.0wt%, based on the total weight of the absorbent solution. In some more preferred embodiments of the present invention, the diazabicyclic acid is present in an amount of 1.0 to 1.5wt%, based on the total weight of the absorbent solution.
In some embodiments of the present invention, the morpholine is present in an amount of 1.5 to 3.0 wt.%, based on the total weight of the absorption liquid. In some embodiments of the present invention, the morpholine may be present in an amount of 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, or 4.0 wt.%, etc., based on the total weight of the absorption liquid. In some preferred embodiments of the present invention, the morpholine is present in an amount of 2.0 to 2.5wt%, based on the total weight of the absorption liquid.
In some embodiments of the invention, the additive comprises sodium molybdate, sodium sulfite, and ethylene glycol.
In the present invention, the additive may function as an antioxidant, a corrosion inhibitor, an anticorrosive agent, and the like. The comprehensive performance of the absorption liquid can be further improved by adding the additive, for example, the absorption liquid has the performance of scale inhibition and corrosion inhibition.
In some embodiments of the present invention, the sodium molybdate is present in an amount of 0.2 to 0.3wt% based on the total weight of the absorbent solution.
In other embodiments of the present invention, the sodium sulfite is present in an amount of 0.1 to 0.2wt%, based on the total weight of the absorbent solution.
In some embodiments of the present invention, the ethylene glycol is present in an amount of 0.3 to 0.5wt%, based on the total weight of the absorbent solution. In some embodiments of the present invention, the content of the ethylene glycol may be 0.3wt%, 0.4wt%, 0.5wt%, or the like, based on the total weight of the absorbent solution. In some preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4 to 0.5wt%, based on the total weight of the absorbent solution. In some most preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4wt%, based on the total weight of the absorption liquid.
In a second aspect of the present invention, there is provided a method for producing an absorbent liquid according to the first aspect of the present invention, comprising: mixing triazine, hindered amine and additive with water to obtain the absorption liquid.
In some embodiments of the present invention, the triazine content in the absorption liquid is 10 to 18wt% in terms of weight percentage; the content of the sterically hindered amine is 1 to 5wt%, preferably 2.5 to 4wt%; the content of the additive is 0.1-1 wt%, preferably 0.6-0.8 wt%.
In some embodiments of the invention, the triazine content in the absorption liquid may be 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, or the like, in weight percent. In some preferred embodiments of the present invention, the triazine content in the absorption liquid is 13 to 15wt% in weight percentage.
In some embodiments of the invention, the triazine is 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
In other embodiments of the present invention, the hindered amine comprises at least one of diazabicyclo and morpholine, preferably diazabicyclo and morpholine.
The inventor of the present application found through research that the H pair of the absorption liquid can be increased by adding the sterically hindered amine to the absorption liquid 2 The amount of S absorbed and the rate of S absorption. Further, when the hindered amine includes both diazabicyclo and morpholine, the absorption performance of the absorption liquid may be optimized.
In some embodiments of the invention, the diazabicyclo ring is present in an amount of 0.5 to 4.0wt%, based on the total weight of the absorption liquid. In some embodiments of the invention, the diazabicyclo ring may be present in an amount of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 3.0wt%, 4.0wt%, or the like, based on the total weight of the absorption liquid. In some preferred embodiments of the present invention, the diazabicyclic acid is present in an amount of 1.0 to 2.0wt%, based on the total weight of the absorbent solution. In some more preferred embodiments of the present invention, the diazabicyclic acid is present in an amount of 1.0 to 1.5wt%, based on the total weight of the absorbent solution.
In some embodiments of the present invention, the morpholine is present in an amount of 1.5 to 3.0 wt.%, based on the total weight of the absorption liquid. In some embodiments of the present invention, the morpholine may be present in an amount of 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, or 4.0 wt.%, etc., based on the total weight of the absorption liquid. In some preferred embodiments of the present invention, the morpholine is present in an amount of 2.0 to 2.5wt%, based on the total weight of the absorption liquid.
In some embodiments of the invention, the additive comprises sodium molybdate, sodium sulfite, and ethylene glycol.
In the present invention, the additive may function as an antioxidant, a corrosion inhibitor, an anticorrosive agent, and the like. The comprehensive performance of the absorption liquid can be further improved by adding the additive.
In some embodiments of the present invention, the sodium molybdate is present in an amount of 0.2 to 0.3wt% based on the total weight of the absorbent solution.
In other embodiments of the present invention, the sodium sulfite is present in an amount of 0.1 to 0.2wt%, based on the total weight of the absorbent solution.
In some embodiments of the present invention, the ethylene glycol is present in an amount of 0.3 to 0.5wt%, based on the total weight of the absorbent solution. In some embodiments of the present invention, the content of the ethylene glycol may be 0.3wt%, 0.4wt%, 0.5wt%, or the like, based on the total weight of the absorbent solution. In some preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4 to 0.5wt%, based on the total weight of the absorbent solution. In some most preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4wt%, based on the total weight of the absorbent solution.
In some embodiments of the invention, the method specifically comprises: weighing the required amount of triazine, hindered amine and additive; and then mixing the substances with water, and stirring until the substances are dissolved to obtain the absorption liquid.
In a third aspect, the invention provides an absorption solution prepared by the method of the first aspect or the absorption solution prepared by the method of the second aspect, and H in a sulfur-containing gas 2 Application in the removal of S.
In some embodiments of the invention, the sulfur-containing gas comprises H, based on the total volume of the gas 2 The volume fraction of S is less than 2.0%.
In other embodiments of the present invention, the sour gas comprises at least one of sour natural gas and sour oilfield associated gas.
The invention has the beneficial effects that: compared with the traditional desulfurization absorption liquid, the invention removes H 2 The S absorption liquid has high sulfur removal efficiency, large sulfur capacity and small using amount, and simultaneously has the performance of scale inhibition and corrosion inhibition, thereby achieving the purpose of improving economic benefit.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
The measurement methods used in the following examples are as follows:
and (3) measuring sulfur capacity: the raw material gas is composed of H 2 S and N 2 A mixture of compositions in which H 2 The volume fraction of S is 0.15%, the pressure is 2.5MPa, and the temperature is 40 ℃. 300ml was freed of H 2 And (4) adding the absorption liquid of the S into a cavity of the high-pressure reaction kettle, and controlling the temperature of the absorption liquid by the reaction kettle through the heat conduction oil in the jacket. Introducing H into a high-pressure reaction kettle 2 The sulfur capacity was measured by bubbling the raw gas of S. During the test, the flow rate of the raw material gas is 600mL/min, and zinc acetate solution with the mass fraction of 2% is introduced into a purified gas outlet. And starting timing when the feed gas is introduced, and stopping introducing the feed gas when the zinc acetate solution turns white obviously.
And (3) corrosion inhibition performance determination: by referring to national standard JB/T7901-2001 metal material laboratory homogeneous corrosion complete immersion test method and oil and gas industry standard SY/T5273-2000 corrosion inhibitor performance evaluation method for oilfield produced water of metal material, a coupon test is adopted to remove H 2 And (4) measuring the corrosion inhibition performance of the absorption liquid of the S. The method comprises the following operation steps: 1) 300mL of high-salt mine water is added into the reaction kettle cavity, and 300mL of H removal water is added during a comparative test 2 S, absorbing liquid, and blank group is not added; 2) Placing 2 hanging pieces made of the same material in a reaction kettle, and ensuring that the hanging pieces are completely immersed in a corrosive medium and do not contact the wall surface of the reaction kettle; 3) Filling high-pressure nitrogen (replaced by purified gas standard gas) into the reaction kettle to the test pressure; 4) Heating the reaction kettle to 80 ℃ through heat conducting oil, and timing after the preset temperature is reached. After the test is carried out for 72 hours or more, the pressure is relieved, the hanging piece is taken out, the corrosion condition is observed, and whether cracks and pot holes exist is particularly noticed. Immediately washing with desalted water after observation, scrubbing with soft brush or hard rubber, removing corrosion product with soft surface layer, gradually cleaning with acetone and anhydrous ethanol, blow drying with cold air, wrapping with filter paper, drying in a drier for 1 hrWeighed to the nearest 0.0001g. Hanging piece treatment process: 1) The material of the hanging piece to be processed is 304, the hanging piece is polished by water grinding sand paper with the mesh size of not less than 120 meshes to 2000 meshes, the mesh size of the water grinding sand paper is from low to high during polishing, rust, spots and burrs are removed, and the surface of the hanging piece is polished to be bright and has no trace; 2) Clamping with forceps, cleaning in petroleum ether or acetone, and removing oily protective film on the surface; 3) Measuring the size by using a vernier caliper; 4) Soaking in anhydrous ethanol for about 1 minute, taking out, air drying, wrapping with filter paper, drying for 1 hr, weighing with balance, weighing to 0.0001g, and storing in a dryer.
And (3) determining the scale inhibition performance: the scale formation is mainly CaCO 3 And the scale inhibition performance test is carried out according to GB/T16632-2019 calcium carbonate deposition method for measuring the scale inhibition performance of the water treatment agent. The method comprises the following operation steps: the method comprises the steps of preparing a test solution from prepared water containing a certain amount of bicarbonate radicals and calcium ions and a scale inhibitor, accelerating the decomposition of calcium bicarbonate into calcium carbonate at the temperature of 80 +/-1 ℃, measuring the calcium ion concentration in the test after the calcium carbonate is balanced, and determining the scale inhibition performance of the scale inhibitor when the calcium ion concentration is higher. Removal of H 2 The scale inhibition performance of the absorption liquid of S is calculated by eta, the numerical value is expressed by percent, and the scale inhibition performance is calculated according to the following formula:
Figure BDA0003103645330000061
in the formula:
rho 0 is the numerical value of the mass concentration of calcium ions in a prepared water sample, and the unit is mg/mL;
rho 1-without addition of H 2 S, preparing a numerical value of the mass concentration of calcium ions in a water sample by using the absorption liquid, wherein the unit is mg/mL;
rho 2-addition of H 2 And (3) preparing a numerical value of the mass concentration of calcium ions in the water sample of the absorption liquid of S, wherein the unit is mg/mL.
The specific operation steps are as follows:
(1) 1mL of sodium bicarbonate standard solution of about 18.3mg HCO was prepared 3 - And 1mL of about 6mgCa 2+ A standard solution of calcium chloride;
(2) preparing hydrochloric acid standard titration solution with about 0.1mol/L and ethylenediaminetetraacetic acid (EDTA) standard titration solution with about 0.01mol/L, and preparing borax buffer solution with pH value of about 9, bromocresol green-methyl red indicator and calcium-carboxylic acid indicator;
(3) preparation and removal of H 2 Test of the absorption liquid of S with calcium ion-containing water sample: adding 250mL of water into a 500-volume flask, and adding a certain volume of calcium chloride standard solution by using a burette to ensure that the amount of calcium ions is 120mg; adding a certain amount of hydrogen to remove H by using a pipette 2 Shaking up the absorption liquid of S; then adding 20mL of borax buffer solution, and shaking up; slowly adding sodium bicarbonate standard solution with a certain volume into a burette to enable the quantity of bicarbonate ions to be 366mg, diluting with water to scale, and shaking up;
(4) preparing a blank test water sample containing calcium ions: the procedure was the same as in (3) except that H removal was not added 2 An absorption liquid of S;
(5) removing H from the solution 2 Respectively placing a calcium ion-containing water sample for testing the absorption liquid of the S and a calcium ion-containing water sample for a blank test in two clean conical bottles, immersing the bottles in a constant-temperature water bath at the temperature of 80 +/-1 ℃, and placing the bottles at the constant temperature for 10 hours; after the reaction is finished, dry-filtering the hot mixture by using medium-speed quantitative filter paper; after the filtrate is cooled, taking 25mL of the filtrate in a conical bottle, adding water to about 80mL, adding 5mL of 200g/L potassium hydroxide solution and about 0.1g of calcium-carboxylic acid indicator; titrating the solution with EDTA standard solution until the solution changes from purple red to bright blue as the end point, and calculating the content of the removed H 2 The scale inhibition rate is calculated by the formula according to the calcium ion concentration in the calcium ion-containing water sample for the test of the absorption liquid of S and the calcium ion concentration in the calcium ion-containing water sample for the blank test.
Example 1
10g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 85.4g of water, and after stirring until dissolved, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite and 0.3wt% ethylene glycol.
Example 2
10g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.0g of diazabicyclo, 1.5g of morpholine, 0.2g of sodium molybdate, 0.2g of sodium sulfite and 0.4g of ethylene glycol were added to 86.7g of water, and after stirring until dissolved, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprises: 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.0wt% diazabicyclo, 1.5wt% morpholine, 0.2wt% sodium molybdate, 0.2wt% sodium sulfite and 0.4wt% ethylene glycol.
Example 3
15g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 80.4g of water, and after stirring until dissolution, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprised 15wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite and 0.3wt% ethylene glycol.
Example 4
10g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 0.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 86.4g of water, and after stirring until dissolved, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 0.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite and 0.3wt% ethylene glycol.
Example 5
10g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5g of diazabicyclo, 1.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 86.4g of water, and after stirring until dissolved, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 1.5wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite and 0.3wt% ethylene glycol.
Example 6
1.5g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazineDiazabicyclo, 2.5g morpholine, 0.3g sodium molybdate, 0.1g sodium sulfite and 0.3g ethylene glycol were added to 85.3g water and stirred until dissolved to obtain dehydro-H 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.3wt% sodium molybdate, 0.1wt% sodium sulfite and 0.3wt% ethylene glycol.
Example 7
10g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.2g of sodium sulfite and 0.3g of ethylene glycol were added to 85.3g of water, and after stirring until dissolved, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.2wt% sodium sulfite, and 0.3wt% ethylene glycol.
Example 8
10g of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.4g of ethylene glycol were added to 85.3g of water, and after stirring until dissolved, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite and 0.4wt% ethylene glycol.
Example 9
1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine (10g), diazabicyclo (4 g), sodium molybdate (0.2 g), sodium sulfite (0.1 g) and ethylene glycol (0.3 g) were added to water (85.4 g), and after stirring to dissolve, H was removed 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 4.0wt% diazabicyclo, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite and 0.3wt% ethylene glycol.
Example 10
1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine (10g), morpholine (4 g), sodium molybdate (0.2 g), sodium sulfite (0.1 g) and ethylene glycol (0.3 g) were added to water (85.4 g), and after stirring and dissolving, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid comprised 10wt% 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 4.0wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite and 0.3wt% ethylene glycol.
Comparative example 1
13g of 1,3, 5-tris (2-hydroxyethyl) -hexahydros-triazine was added to 87.0g of water, and after stirring and dissolution, H removal was obtained 2 And (3) an absorption liquid of S. The absorption liquid contained 13wt% of 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
Test example 1
Removal of H from the samples obtained in examples 1 to 10 and comparative example 1 2 The sulfur capacity, corrosion inhibition performance and scale inhibition performance of the absorption liquid of S were measured, and the results are shown in tables 1 to 3, respectively.
TABLE 1 removal of H 2 Sulfur capacity of S-absorbing liquid
Figure BDA0003103645330000091
Figure BDA0003103645330000101
TABLE 2 removal of H 2 Corrosion inhibition performance of S absorption liquid (test result of hanging sheet of material 304 under pressure of 3.8-4.4 MPa and temperature of 80 +/-1 ℃ for 72 h)
Serial number Before test (g) After the test (g) Corrosion Rate (mm/a)
Comparison ofExample 1 9.1289 9.1286 0.0035
Example 1 9.0146 9.0144 0.0024
Example 2 7.8306 7.8304 0.0026
Example 3 8.1257 8.1255 0.0023
Example 4 8.1725 8.1723 0.0024
Example 5 7.9562 7.9560 0.0021
Example 6 8.3325 8.3323 0.0027
Example 7 8.8765 8.8763 0.0029
Example 8 8.4526 8.4524 0.0023
Example 9 8.1726 8.1724 0.0027
Example 10 8.1733 8.1731 0.0025
TABLE 3 removal of H 2 Scale inhibition performance of S absorption liquid
Figure BDA0003103645330000102
Figure BDA0003103645330000111
The results of tables 1 to 3 above show that: compared with the single triazine absorption liquid (comparative example 1), the absorption liquid (examples 1-10) of the invention has the advantages of large sulfur capacity, small dosage, and scale and corrosion inhibition performance.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. For removing H from sulfur-containing gas 2 The absorption liquid of S comprises the following components in percentage by weight:
10 to 18 wt.%, preferably 13 to 15 wt.% of triazine;
1 to 5 wt.%, preferably 2.5 to 4 wt.% of a sterically hindered amine;
0.1 to 1wt%, preferably 0.6 to 0.8wt% of an additive; and
the balance of water.
2. The absorbent solution of claim 1, wherein the triazine is 1,3,5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
3. The absorbent liquid according to claim 1 or 2, wherein the hindered amine comprises at least one of diazabicyclo and morpholine; preferably diazabicyclo and morpholine are included.
4. The absorbent solution according to claim 3, wherein the diazabicyclo ring is present in an amount of 0.5 to 4.0 wt.%, preferably 1.0 to 2.0 wt.%, more preferably 1.0 to 1.5 wt.%, based on the total weight of the absorbent solution; and/or the morpholine content is 1.5-4.0 wt%, preferably 2.0-2.5 wt%.
5. The absorption liquid according to any one of claims 1 to 4, wherein the additive comprises sodium molybdate, sodium sulfite and ethylene glycol.
6. The absorption liquid according to claim 5, wherein the sodium molybdate is contained in an amount of 0.2 to 0.3wt% based on the total weight of the absorption liquid; and/or the content of sodium sulfite is 0.1-0.2 wt%; and/or the content of the ethylene glycol is 0.3-0.5 wt%, preferably 0.4-0.5 wt%.
7. A method for producing an absorbent liquid according to any one of claims 1 to 6, which comprises: mixing triazine, hindered amine and additive with water to obtain the absorption liquid.
8. An absorption liquid according to any one of claims 1 to 6 or prepared by the method according to claim 7 in a sulfur-containing gas, H 2 Application in the removal of S.
9. Use according to claim 8, wherein the sulfur-containing gas comprises H, based on the total volume of the gas 2 The volume fraction of S is less than 2.0%.
10. The use of claim 8 or 9, wherein the sour gas comprises at least one of sour natural gas and sour oilfield associated gas.
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